CN105339300B

CN105339300B - Method for producing carbon nanotubes

Info

Publication number: CN105339300B
Application number: CN201480035862.6A
Authority: CN
Inventors: 涉谷明庆
Original assignee: Nippon Zeon Co Ltd
Current assignee: Zeon Corp
Priority date: 2013-06-27
Filing date: 2014-06-26
Publication date: 2017-05-24
Anticipated expiration: 2034-06-26
Also published as: US9499904B2; JP6428613B2; JPWO2014208097A1; CN105339300A; US20160273100A1; KR20160024871A; EP3015425A4; EP3015425A1; WO2014208097A1

Abstract

A method for producing carbon nanotubes according to the present invention comprises a growth step of growing CNTs on a base material (12) and a cleaning step of supplying a water-containing cleaning gas into a growth furnace (13) to perform cleaning, wherein the cleaning is performed in the cleaning step in such a manner that the formula: 0.7 <= (2[CO2]+[CO])/[H2] <= 1.3 can be satisfied wherein [H2], [CO2] and [CO] respectively represent the concentrations of hydrogen, carbon dioxide and carbon monoxide in a gas contained in the growth furnace (13).

Description

The manufacture method of CNT

Technical field

The present invention relates to the manufacture method of CNT.

Background technology

Using chemical vapour deposition technique (hereinafter also referred to as " CVD ") etc. manufacture CNT (hereinafter also referred to as " CNT ") when, the carbon system accessory substance that carbon included in adhering to by unstrpped gas in manufacture stove sometimes etc. is constituted is (below, also referred to as It is " carbon dirt ").Method as such carbon dirt is removed, it is known to the method described in patent document 1~3.

Recorded in patent document 1 and supplied in the reaction tube used in the manufacture to CNT steam so as to carbon dirt be gasified Method.Introducing carbon dioxide in the reacting furnace used in the manufacture to carbon fiber is recorded in patent document 2, by making carbon Dirt and carbon dioxide reaction, the method for making carbon dirt be discharged as CO gas.Recorded in patent document 3 and used bag The method that clean gas containing oxygen atom remove the carbon dirt in growth furnace.

In addition, recorded in patent document 4 there occurs charing by being infiltrated in the heat-insulating material in carburizer The injection air such as the carbon method that is burnt out and be removed.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2003-146633 publications

Patent document 2：Japanese Unexamined Patent Publication 2006-315889 publications

Patent document 3：Japanese Unexamined Patent Publication 2012-250862 publications

Patent document 4：Japanese Unexamined Patent Publication 2007-131936 publications

The content of the invention

Problems to be solved by the invention

When CNT is manufactured by CVD, carbon can be impregnated into the inside (carburizing) of furnace wall and furnace interior part sometimes.In addition, such as Fruit carburizing is further exceedingly carried out, then the tissue near the top layer of furnace wall and furnace interior part may be triggered brittle, amorphous carbon, The carbon such as graphite, metal-carbide dirt comes off from top layer or peels off problem as (excess carburizing).Rule of thumb understand, excess carburizing The replacing construction of body of heater and furnace interior part can not only be accelerated, it is also possible to cause the carbon dirt for coming off to be mixed into product, cause CNT systems The decline of the amount of making and the deterioration of CNT qualities.

But, if in order to prevent excess carburizing and excessive cleaning, can exist cause stove material because cleaning is excessive The problem for itself aoxidizing.

Clean condition is confirmed without record in patent document 1, in addition, also not accounting for excessively causing due to cleaning Stove material oxidation.

Recorded in patent document 2 by the temperature change in cleaning, weight change or pressure change or by cleaning Carbon monoxide gas concentration of generation etc. is measured to confirm clean condition.But in patent document 2, due to do not consider by The oxidation of stove material caused by cleaning is excessive, therefore the result of said determination cannot be based on and solve these problems.

Additionally, having been recorded in patent document 3 in continuous manufacture CNT, cleaned in the quality reduction of CNT, but Do not consider due to the oxidation of the excessive caused stove material of cleaning.

Further, at the end of monitoring gas concentration lwevel and oxygen concentration have been recorded in patent document 4 to judge cleaning Between, but do not consider due to the oxidation of the excessive caused stove material of cleaning.In addition, patent document 4 does not record the manufacture of CNT.

The present invention be in view of such problem and complete, it is therefore intended that offer is prevented from causing because cleaning is excessive Stove material oxidation CNT manufacture method.

The method of solve problem

In order to solve the above problems, the manufacture method of CNT of the present invention is to make CNT in area load There is the method grown on the base material of catalyst, wherein, the manufacture method includes：To the institute of the base material being sent in growth furnace State catalyst and supply the unstrpped gas of CNT, and at least one of the catalyst and the unstrpped gas are carried out Heating, makes the growth operation that CNT grows on the substrate；With the cleaning gas that water is included to supply in the growth furnace Body, to the cleaning process cleaned in the growth furnace, the concentration of the hydrogen in gas in by the growth furnace is set to [H₂], the concentration of carbon dioxide be set to [CO₂], the concentration of carbon monoxide is when being set to [CO], in the cleaning process, to described Cleaned in growth furnace, so that meeting following formula (1)：0.7≤{(2[CO₂]+[CO])/[H₂]}≤1.3···(1)。

It should be noted that in the manufacture method of CNT of the present invention, preferably in the growth operation, To the catalyst of the base material activation of catalyst material is also supplied in addition to supplying the unstrpped gas.

In addition, in the manufacture method of CNT of the present invention, more preferably to described in the cleaning process Cleaned in growth furnace, so that meeting following formula (2)：0 ＜ ([CO]/[CO₂])≤10···(2)。

Further, in the manufacture method of CNT of the present invention, at least one of more preferably described growth furnace Subpackage contains metal.

In addition, in the manufacture method of CNT of the present invention, more preferably described cleaning process is included to described (2 [CO in growth furnace₂]+[CO])/[H₂] be monitored.

Further, in the manufacture method of CNT of the present invention, more preferably described cleaning process is included to institute State [CO]/[CO in growth furnace₂] be monitored.

The effect of invention

The present invention is due to carrying out the hydrogen during cleaning causes the gas in growth furnace, carbon dioxide and an oxidation to growth furnace The concentration of carbon in specific scope, therefore, it is possible to prevent due to cleaning it is excessive caused by stove material oxidation.

Brief description of the drawings

Fig. 1 is schematic diagram, shows the manufacture device used in the manufacture method that one embodiment of the present invention is related to One.

Fig. 2 is schematic diagram, shows the manufacture device used in the manufacture method that one embodiment of the present invention is related to Other examples.

Fig. 3 is the coordinate diagram of the relation between moisture concentration and gas concentration in the cleaning process for show reference example 1.

Fig. 4 is the coordinate diagram of the relation between cleaning temp and gas concentration in the cleaning process for show reference example 1.

Fig. 5 is the coordinate diagram of the relation between moisture concentration and gas concentration in the cleaning process for show reference example 2.

Fig. 6 is the coordinate diagram of the relation between cleaning temp and gas concentration in the cleaning process for show reference example 2.

Fig. 7 is the coordinate diagram of the relation between cleaning time and gas concentration in the cleaning process for show embodiment.

Fig. 8 is between the carburizing amount in the cumulative operational time and growth furnace of manufacture device that are used in embodiment that shows The coordinate diagram of relation.

Fig. 9 is to show relation between the cumulative operational time of manufacture device that is used in embodiment and manufacturing time accounting Coordinate diagram.

Symbol description

10 CNT manufacture devices

12 base materials

13 growth furnaces

14 heaters

15 gas introduction ports

16 gas discharge outlets

100 CNT manufacture devices

Specific embodiment

Hereinafter, embodiments of the present invention are described in detail.The manufacture method of CNT of the present invention It is the manufacture method for making CNT have the CNT grown on the base material of catalyst in area load.The manufacture method of CNT includes growth work Sequence and cleaning process.

[growth operation]

In operation is grown, the unstrpped gas of CNT and optional is supplied to the catalyst of the base material being sent in growth furnace Activation of catalyst material, and at least one of catalyst and unstrpped gas are heated, CNT is grown on base material. That is, in operation is grown, for example, CNT is made to be grown on base material by chemical vapor deposition (CVD) method.Grown in operation is grown CNT be preferably CNT orientation aggregation, more preferably grown in the way of being vertically oriented with base material CNT orientation aggregation.

(CNT is orientated aggregation)

CNT orientation aggregations are the structure that the numerous CNT grown from base material there occurs orientation along specific direction.

CNT orientation aggregation preferred BET specific surface area be in the case where CNT is mainly not opening CNT 600m²/ more than g, more preferably 800m²/ more than g.BET specific surface area is higher, can more control metal impurities or carbon impurity In the level of the tens of percentages (40% or so) less than weight, therefore preferably.

The weight density of CNT orientation aggregations is preferably 0.002g/cm³Above and 0.2g/cm³Below.If weight density In 0.2g/cm³Hereinafter, then the CNT combinations to each other for constituting CNT orientation aggregations die down, therefore CNT is taken in a solvent etc. When being stirred to aggregation, easily it is uniformly dispersed CNT.That is, by making weight density in 0.2g/cm³Hereinafter, it is easy to obtain To the dispersion liquid of homogeneous.In addition, if weight density is in 0.002g/cm³More than, then CNT can be made to be orientated the one of aggregation Property improve, it is at random to suppress CNT, therefore operation becomes easy.

Preferably there is high-orientation along the CNT orientation aggregations that specific direction is orientated.Here, described " there is high-orientation " Refer to meet at least one of following (1)~(3).

(1) from the 1st direction parallel to CNT length directions and perpendicular to the 1st direction the 2nd direction incident X-rays simultaneously In the case of determining X-ray diffraction intensity (θ -2 θ methods), there is the reflected intensity from the 2nd direction than from the anti-of the 1st direction The big θ angles of intensity and reflection orientation are penetrated, and there is the reflected intensity from the 1st direction than the reflected intensity from the 2nd direction Big θ angles and reflection orientation.

(2) using the two-dimentional diffraction from obtained from perpendicular to the direction of CNT length directions (the 2nd direction) incident X-rays In the case that collection of illustrative plates is to determine X-ray diffraction intensity (Laue method (Laue method)), it may appear that show what anisotropy was present Diffraction peak pattern.

(3) when using the X-ray diffraction intensity obtained using θ -2 θ methods or Laue method, Herman orientation factor is more than 0 And below 1, more preferably 0.25 less than 1.

It is also preferable to have following characteristics：In above-mentioned X-ray diffraction method, the accumulation body between single wall CNT is belonged to (packing) (CP) diffraction maximum and the diffracted intensity at (002) peak and the carbon six-membered ring structure for belonging to composition single wall CNT (100), the degree of the diffraction peak intensity of each incident direction in parallel (the 1st direction) at (110) peak and vertical (the 2nd direction) is mutual not It is identical.

In order that CNT orientation aggregation display high orientation and high-specific surface area, the height of preferably CNT orientation aggregations (length) more than 10 μm and below 10cm scope.When being highly more than 10 μm, orientation is improved.In addition, if height exists Below 10cm, then due to that can carry out the generation of CNT in the short time, therefore, it is possible to suppress the attachment of carbon system impurity, can improve and compare table Area.

Composition CNT is orientated the G/D ratios of the CNT of aggregation preferably more than 3, more preferably more than 4.G/D ratios are to evaluate Usually used index during the quality of CNT.Be can observe in the Raman spectrum of the CNT determined using Raman spectroscopic apparatus and claimed It is G bands (1600cm^-1Near) and D bands (1350cm^-1Near) vibration mode.G bands are come from as the barrel surface of CNT The vibration mode of the hexagonal lattice structure of graphite, D bands come from the vibration mode of amorphous spots.Thus, the peak of G bands and D bands Strength ratio (G/D ratios) is higher, then can more be evaluated as crystallinity CNT high.

(CNT manufacture devices)

Reference picture 1, opposite operation long is described in detail.Fig. 1 shows to be related in one embodiment of the present invention The schematic diagram of of the manufacture device used in manufacture method.CNT manufacture devices 10 possess：Growth furnace 13, heater 14, gas Body introducing port 15 and gas discharge outlet 16.Further, the base material 12 of CNT growth is made to be fed in growth furnace 13.

CNT manufacture devices 10 are that following formation process and growth operation are carried out in the stove (growth furnace 13) in batches The manufacture device of formula.In CNT manufacture devices 10, can from gas introduction port 15 carry out formation process and growth operation in it is necessary The supply of gas etc..So, have the advantages that more equably form the layer of catalyst on substrate.

By realizing growth operation in CNT manufacture devices 10, the surrounding environment of catalyst can be made to turn into unstripped gas While body environment, at least one of catalyst and unstrpped gas are heated, thus make CNT growth.

In operation is grown, the unstrpped gas and activation of catalyst of CNT are being supplied to the growth furnace 13 for being fed into base material 12 After material, or while base feed gas and activation of catalyst material, CNT is set to give birth on the base substrate 12 by CVD It is long.It should be noted that activation of catalyst material can not also be used in operation is grown, but by operation is grown There is activation of catalyst material in the atmosphere for making the growth response for carrying out CNT, can further improve CNT production efficiency and Purity.

When being heated at least one of catalyst and unstrpped gas, more preferably the rwo is heated.It is right In making the reaction temperature of CNT growth, it may be considered that species and concentration and reaction pressure of catalyst and unstrpped gas etc. and fit Locality determines, but is preferably set to so that the activation of catalyst material of the accessory substance for excluding the reason for being inactivated as catalyst Effect be able to the temperature range for fully demonstrating.That is, as most preferred temperature range, can be removed with activation of catalyst material The temperature of the accessory substances such as amorphous carbon, graphite is lower limit, and the CNT as principal product will not be aoxidized by activation of catalyst material Temperature be higher limit.Therefore, can be given birth to as long as carrying out heating-up temperature CNT at least one of catalyst and unstrpped gas Temperature long, preferably more than 400 DEG C and less than 1100 DEG C, more preferably more than 600 DEG C and less than 900 DEG C.Above-mentioned When in temperature range, advantageously showing for activation of catalyst material can be made, and activation of catalyst can be suppressed Material reacts with CNT.

Pressure in growth operation in growth furnace 13 is preferably 10²More than Pa and 10⁷Pa (100 atmospheric pressure) below, enters one Step is preferably 10⁴More than Pa and 3 × 10⁵Pa (3 atmospheric pressure) is below.

As long as the material of raw material of the unstrpped gas as CNT, has raw material for example, under the growth temperature of CNT The gas of carbon source.Wherein, the hydrocarbon such as optimization methane, ethane, ethene, propane, butane, pentane, hexane, heptane, propylene and acetylene, Due to can efficiently manufacture CNT, therefore particularly preferably ethene.In addition, unstrpped gas can also be that methyl alcohol, ethanol etc. are low The gas of level alcohol.The mixture of these gases can also be used.In addition, unstrpped gas can also be carried out through inactive gas it is dilute Release.

As inactive gas, as long as at a temperature of CNT growth torpescence, will not reduce catalyst activity and And the gas not reacted with the CNT of growth.For example, helium, argon gas, nitrogen, neon and Krypton etc. can be enumerated, and Their mixed gas, particularly preferred nitrogen, helium, argon gas and their mixed gas.

As activation of catalyst material, more preferably containing aerobic material, further preferably under the growth temperature of CNT not Badly damaged material can be caused to CNT.For example, water, oxygen, ozone, sour gas, nitrogen oxide；Carbon monoxide and carbon dioxide Deng the oxygenatedchemicals of low carbon atom number；The alcohols such as ethanol, methyl alcohol；The ethers such as tetrahydrofuran；The ketones such as acetone；Aldehydes；Esters； And their mixture is effective.Wherein, as activation of catalyst material, preferably water, oxygen, carbon dioxide, carbon monoxide, Ethers, particularly preferred water and carbon dioxide.

The addition of activation of catalyst material is not particularly limited, activation of catalyst material be water in the case of, with Volumetric concentration meter in the surrounding environment of catalyst, preferably in more than 10ppm and below 10000ppm, more preferably 50ppm with Upper and below 1000ppm, further preferably in more than 100ppm and the scope of below 700ppm.In addition, in activation of catalyst thing In the case that matter is carbon dioxide, the concentration of the carbon dioxide in catalyst surrounding environment is preferably 0.2~70 volume %, more excellent Elect 0.3~50 volume %, more preferably 0.7~20 volume % as.

The mechanism that activation of catalyst material plays desired function is presumed as follows at present.In the growth course of CNT, if Amorphous carbon and graphite for producing secondaryly etc. are attached to catalyst, then catalyst can be caused to inactivate and the growth of CNT is hindered.But , it can be said that if there is activation of catalyst material, then amorphous carbon and graphite etc. can be made to be oxidized to carbon monoxide and titanium dioxide Carbon etc. and gasify, thus show cleaning catalyst, improve catalyst activity and extension active lifetime effect (catalysis Agent activation).

It should be noted that the such compound containing carbon and oxygen of such as alcohols, carbon monoxide etc., can not only be used for raw material Gas, can also be played a role as activation of catalyst material.For example, these compounds and ethene etc. are susceptible to decompose When unstrpped gas as carbon source is applied in combination, these contain carbon and the compound of oxygen can play work as activation of catalyst material With.Furthermore it is possible to speculate, what the compound containing carbon and oxygen and water isoreactivity activation of catalyst combinations of substances high were used In the case of, the compound containing carbon and oxygen will play a role as unstrpped gas.Further, for carbon monoxide etc., thus it is speculated that Its decompose produced by carbon atom will turn into CNT growth response carbon source and oxygen atom then also serve as oxidation amorphous carbon and Graphite etc. and the activation of catalyst material that is gasified play a role.

Growth operation is preferably carried out in high carbon concentration environment.The high carbon concentration environment refers to the ring around catalyst The volume ratio of unstrpped gas is 2~20% or so growth gasses atmosphere in border.Particularly exist in activation of catalyst material Under, because catalysis activity can be significantly improved, therefore, even if catalyst will not also be inactivated under high carbon concentration environment, can be grown The CNT growth of time, and the speed of growth significantly improves.But, in high carbon concentration environment, compared with low carbon concentration environment, Easily in furnace wall etc., largely attachment carbon is dirty.According to manufacture method of the present invention, due to the growing environment of CNT can be kept In the environment being best suitable for, thus can anti-blocking dirt attachment, efficiently manufacture the CNT of high-quality.

Next, the base material 12 used in opposite operation long is illustrated.Base material 12 is have CNT growth in its area load The material of the catalyst of reaction.

The component of base material 12 is constituted, as long as can be in the component of the catalyst of its area load CNT growth reaction Can, preferably more than 400 DEG C at a high temperature of can also keep shape.As its material, for example, can enumerate：Iron, nickel, chromium, molybdenum, Metals such as tungsten, titanium, aluminium, manganese, cobalt, copper, silver, gold, platinum, niobium, tantalum, lead, zinc, gallium, indium, germanium and antimony and comprising these metals Alloy and oxide；Silicon, quartz, glass, mica, graphite and diamond etc. are nonmetallic；And ceramics etc..Metal due to it is non- Metal and ceramic phase are more relatively low than cost, therefore preferably, particularly preferred Fe-Cr (iron-chromium) alloy, Fe-Ni (iron-nickel) alloy, Fe- Cr-Ni (iron-chromium-nickel) alloy etc..

The form of substrate can enumerate tabular, film-form, block or powdered etc..Especially with respect to table for volume The big tabular or powdered of ratio shared by area, is favourable in the case of a large amount of manufacture CNT.

In the case where flat-shaped substrate is used as base material, the thickness of substrate is not particularly limited, for example can be used from Substrate of the several μm of films of degree to number cm degree.The thickness of substrate is preferably more than 0.05mm and below 3mm.If the thickness of substrate It is below 3mm to spend, then fully can heat substrate in CVD operations, can suppress the undergrowth of CNT, and can reduce substrate Cost.If the thickness of substrate is more than 0.05mm, the deformation of the substrate that carburizing causes can be suppressed, and due to being difficult to cause The flexure of substrate itself, therefore conveying to substrate and recycling are favourable.It should be noted that the carburizing of substrate refers to carbon Composition infiltrates into substrate.

The shape of the flat-shaped substrate used as base material, size are not particularly limited, used as shape, it is possible to use rectangular Shape or foursquare substrate.Size to substrate one side is not particularly limited, from from the viewpoint of the production of CNT, it is more big more It is preferred that.According to the present invention, large-scale substrate can be suitably used.For example, according to the present invention, can one side be more than 100mm and CNT is more equably manufactured on the substrate of below 1000mm.

Formed at least any one side that can also be in the surface of the flat-shaped substrate used as base material and the back side and oozed Carbon prevents layer.It is preferred that carburizing is formed on surface and this two sides of the back side prevents layer.It is for preventing in growth that the carburizing prevents layer The protective layer that substrate deforms by carburizing in operation.

Carburizing prevents layer to be preferably made up of metal or ceramic material, particularly preferably prevents effect ceramic material high by carburizing Constitute.As metal, copper and aluminium etc. can be enumerated.As ceramic material, can for example enumerate aluminum oxide, silica, zirconium oxide, The oxides such as magnesia, titanium oxide, silica-alumina, chromium oxide, boron oxide, calcium oxide, zinc oxide；Aluminium nitride, nitridation The nitride such as silicon.Wherein, aluminum oxide, silica prevent effect high due to carburizing, so it is preferred that.

Catalyst is loaded with base material, and (be formed with base material in the case that carburizing prevents layer prevents negative on layer in carburizing It is loaded with catalyst).As catalyst, such as iron, nickel, cobalt, molybdenum and their chloride and alloy can be enumerated and they enter One step and aluminium, aluminum oxide, titanium oxide, titanium nitride, silica Composite are formed as the catalyst of stratiform.For example, conduct Catalyst, can enumerate：Iron-molybdenum film, aluminum oxide-iron thin film, aluminum oxide-cobalt thin film and aluminum oxide-iron-molybdenum film, aluminium-iron Film, aluminium-iron-molybdenum film etc..As the amount of catalyst, can manufacture in the range of CNT.For example using iron In the case of, the film forming thickness of iron thin film is preferably more than 0.1nm and below 100nm, more preferably more than 0.5nm and below 5nm, special Not preferred more than 0.8nm and below 2nm.

When substrate surface forms catalyst, it is possible to use any technique in wet process or dry process.It is specific and Speech, it is possible to use sputtering vapour deposition method is coated based on the liquid to metal particle to be scattered in appropriate solvent, fired Method etc..Patterning techniques alternatively, it is also possible to known photoengraving or nano impression etc. will be employed be applied in combination so as to The catalyst load area for making substrate surface is in arbitrary shape.

In operation is grown, can be according to film forming in the patterning of the catalyst on base material and the growth time of CNT, will The shape of CNT orientation aggregations is arbitrarily controlled to film-form, cylindric, prism-shaped and other complicated shapes etc..Particularly For the CNT orientation aggregations of film-form, compared with its length and width dimensions, thickness (height) size is minimum, but length And width dimensions can be based on the patterning of catalyst and arbitrarily control, thickness can be based on constituting CNT orientation aggregations The growth time of each CNT and arbitrarily control.

The wet process for forming catalyst layer in substrate surface includes：The metal comprising the element as catalyst will be made to be had Machine compound and/or dissolving metal salts are coated on the operation on base material in the coating agent of organic solvent, and to coating The operation that coating agent is heated.The polycondensation reaction for suppressing metallo-organic compound and slaine can be added in coating agent Stabilizer.

Can be using by appointing in the method, spin-coating method, the dip coatings that are coated such as spraying, brushing etc. in painting process Meaning method, but from from the viewpoint of productivity and film thickness monitoring, it is preferred to use dip coating.

It is preferred that carrying out heating process after painting process.Trigger metallo-organic compound and metal by being heated The hydrolysis and polycondensation reaction of salt, cover so as to form the solidification comprising metal hydroxides and/or metal oxide in substrate surface Film.It is preferred that more than about 50 DEG C and less than 400 DEG C of scope, right to heating-up temperature according to the species of the catalyst film to be formed Heat time is more than 5 minutes and the scope of less than 3 hours is suitably adjusted.

For example, in the case where aluminum oxide-iron thin film is formed as catalyst, iron is formed after pellumina is formd Film.

As metallo-organic compound and/or slaine for forming aluminum oxide film, can enumerate：Three aluminium methoxides, The aluminium-alcohol salts such as three aluminium ethylates, three normal propyl alcohol aluminium, aluminum isopropylate, three Tributyl aluminates, three aluminium secondary butylates, three tert-butyl alcohol aluminium.These Material can be used alone or use as a mixture.In addition to the metallo-organic compound comprising aluminium, can also arrange Lift the complex compounds such as aluminium tris(acetylacetonate) (III).As slaine, can enumerate aluminum sulfate, aluminium chloride, aluminum nitrate, aluminium bromide, Silver iodide, aluctyl, basic aluminium chloride, basic aluminum nitrates etc..These compounds can be used alone, it is also possible to which mixing makes Use two or more.Wherein, aluminium-alcohol salt is preferably used.

As metallo-organic compound and/or slaine for forming iron thin film, can enumerate：Iron pentacarbonyl, two cyclopentadienyls Iron, ferric acetyl acetonade (II), ferric acetyl acetonade (III), trifluoroacetylacetone (TFA) iron (II), trifluoroacetylacetone (TFA) iron (III) etc..Make It is slaine, can enumerates for example：The inorganic acid such as ferric sulfate, ferric nitrate, ferric phosphate, iron chloride, ferric bromide iron, ferric acetate, grass Organic acid iron such as sour iron, ironic citrate, ferric lactate etc..These compounds can be used alone, it is also possible to be used in mixed way 2 kinds More than.In these compounds, organic acid iron is preferably used.

Stabilizer is preferably selected from least a kind in beta-diketon and alkanolamine.These compounds can be used alone, and also may be used It is used in mixed way with by two or more.Beta-diketon class includes acetylacetone,2,4-pentanedione, methyl acetoacetate, ethyl acetoacetate, benzoyl third Ketone, dibenzoyl methane, benzoyltrifluoroacetone, furoyl acetone and trifluoroacetylacetone (TFA) etc., particularly preferably use acetyl Acetone, ethyl acetoacetate.Ethyl alcohol amine includes MEA, diethanol amine, triethanolamine, N methyldiethanol amine, N- Ethyldiethanolamine, N, N- dimethylaminoethanols, diisopropanolamine (DIPA), triisopropanolamine etc., preferably use secondary alkanolamine or uncle Alkanolamine.

As organic solvent, it is possible to use the various organic solvents such as alcohol, glycol, ketone, ether, esters, hydro carbons, but have from metal From the viewpoint of the dissolubility of machine compound and slaine is good, alcohol or glycol are preferably used.These organic solvents can individually make With, it is also possible to it is mixed with two or more.Used as alcohol, methyl alcohol, ethanol, isopropanol etc. are excellent in terms of operability, storage stability Choosing.

Growth furnace 13 for making to turn into unstrpped gas environment around base material 12 and protect the stove of unstrpped gas environment, It is the stove that base material 12 is received when CNT growth is made.At least a portion of growth furnace 13 includes metal.The bottom surface of growth furnace 13 into It is the mounting surface of base material 12.When operation is grown, base material 12 is placed with mounting surface.

The side of growth furnace 13 is provided with gas introduction port 15 and gas discharge outlet 16.Gas introduction port 15 and gas are arranged Outlet 16 is set in mutually opposing mode.The gas such as unstrpped gas imported from gas introduction port 15 is from the quilt of gas discharge outlet 16 Discharge.As the mechanism for discharging gas from gas discharge outlet 16, can be suitably in the past public using aspirating mechanisms such as pump etc. The mechanism known.

Heater 14 is heated at least one of catalyst and unstrpped gas.Heater 14 includes being located at growth furnace Heater and the heater above the upside of growth furnace 13 below 13 downside.In addition, CNT manufacture devices 10 are also equipped with Positioned at the side heater of the side of growth furnace 13.That is, heater 14 is set in the way of surrounding around growth furnace 13.

In operation is grown, growth furnace 13 is internally heated from the outside of growth furnace 13 by using heater 14, In the catalyst loaded to the base material 12 being sent in growth furnace 13 and the unstrpped gas being supplied in growth furnace 13 at least One is heated.

As heater 14, as long as the heater that growth furnace 13 is heated can be then not particularly limited, it is excellent The heater that choosing can be heated in 400 DEG C~1100 DEG C of scope, can enumerate for example：Resistance heater, infrared ray add Hot device, induction heater etc..

[cleaning process]

In cleaning process, to clean gas of the supply comprising water in growth furnace 13, to being cleaned in growth furnace 13. In cleaning process, by supplying clean gas in growth furnace 13, making to be attached to the carbon dirt gasification on furnace wall and furnace interior part surface. In addition, making the carbon spread inside carburizing to furnace wall and furnace interior part to outside (also referred to as " decarburization ") and gasifying.That is, described cleaning Refer to make to be attached to the carbon system accessory substances such as the amorphous carbon and graphite on furnace wall and furnace interior part surface (carbon dirt), carburizing to furnace wall And the operation being removed after the carbon gasification inside furnace interior part.

(clean gas)

As long as the gas that clean gas can be cleaned to the furnace wall in growth furnace 13 and furnace interior part, at least Comprising water.In the case where growth furnace 13 is made up of metal, by using the clean gas comprising water, and oxygen is used as cleaning Compared during gas, the generation of the oxidation in growth furnace 13 can be reduced.As clean gas, for example, can use vapor.Separately Outward, clean gas can also include such as inactive gas in addition to the gas comprising water.It is attached in furnace wall and stove from removing From the viewpoint of the carbon dirt of part etc. is such, preferably clean gas do not include carbon atom.

Here, the concentration of the hydrogen in gas in by growth furnace 13 is set to [H₂], the concentration of carbon dioxide is set to [CO₂], the concentration of carbon monoxide is when being set to [CO], in cleaning process, meet to being cleaned in growth furnace 13, being caused：

0.7≤{(2[CO₂]+[CO])/[H₂]}≤1.3···(1)。

It should be noted that concentration [the H of the hydrogen in gas in growth furnace 13 described in cleaning process₂], titanium dioxide Concentration [the CO of carbon₂] and the concentration [CO] of carbon monoxide be volumetric concentration.

It is believed that when using the clean gas comprising water to being cleaned in growth furnace 13, in furnace wall and furnace interior Following 3 kinds of chemical reactions can occur near the top layer of part.

H₂O+C→CO+H₂···(a)

2H₂O+C→CO₂+2H₂···(b)

xH₂O+yM→M_yO_x+xH₂···(c)

(M：Metal；x、y：Arbitrary Digit)

Therefore, in cleaning process, (2 [CO are made by carrying out cleaning in growth furnace 13₂]+[CO])/[H₂] 0.7 with It is upper and less than 1.3 scope, can be while the generation of oxidation reaction of above-mentioned (c) furnace wall and furnace interior part be prevented, suitably Ground removes the carbon dirt in growth furnace 13.In the case where furnace wall and furnace interior part there occurs oxidation, its tissue is rule of thumb understood Carburizing speed improve, but according to the present invention it is possible to prevent by the oxidation of furnace wall and furnace interior part caused by excessive cleaning.Need It is noted that from the viewpoint of chemically measuring, (2 [CO₂]+[CO])/[H₂] 1 is not more than, but in fact, by above-mentioned Chemically react produce hydrogen, there is between carbon monoxide and carbon dioxide generation side reaction etc., it is contemplated that the possibility Property, higher limit is set to 1.3.

In addition, in cleaning process, cleaning is carried out in preferred pair growth furnace 13 so that reaching 0.8≤{ (2 [CO₂]+ [CO])/[H₂]≤1.1 scope, most preferably cause (2 [CO to carrying out cleaning in growth furnace 13₂]+[CO])/[H₂]=1. So that (2 [CO₂]+[CO])/[H₂The mode of]=1 in the preferable cleaning process that is cleaned in growth furnace 13, not occurring on State the oxidation reaction of (c) furnace wall and furnace interior part.

It should be noted that concentration [the H of the hydrogen, carbon dioxide and carbon monoxide in gas in growth furnace 13₂]、[CO₂] And [CO], the material referred in water and growth furnace 13 in the clean gas imported in cleaning process reacted and given birth to Into hydrogen, carbon dioxide and carbon monoxide concentration.For the hydrogen in the gas in growth furnace 13, carbon dioxide and carbon monoxide Whether the material generated for the substance reaction in the water in clean gas and growth furnace 13, can be by the way that clean gas will be imported The concentration of hydrogen, carbon dioxide and carbon monoxide in preceding growth furnace 13 and the hydrogen, the carbon dioxide and that import after clean gas The concentration of carbonoxide is compared to be judged.

When manufacturing CNT using CVD, carbon can infiltrate into the inside (carburizing) of furnace wall and furnace interior part sometimes.In addition, if Carburizing is further exceedingly carried out, then the tissue near the top layer of furnace wall and furnace interior part may be triggered brittle, amorphous carbon, stone The carbon such as ink, metal-carbide dirt comes off from top layer or peels off problem as (excess carburizing).Rule of thumb understand, excess carburizing is not The replacing construction of body of heater and part can only be accelerated, it is also possible to cause the carbon dirt for coming off to be mixed into product, cause CNT manufactures Decline and the deterioration of CNT qualities.That is, even if being cleaned after it there occurs excess carburizing, it is also possible to cannot reply furnace wall and The embrittlement of the tissue of furnace interior part.Furthermore it is possible to carburizing to the carbon (decarburization) in brittle tissue is removed by cleaning, but root According to experience, carburizing can earlier occur in the brittle growth operation being organized in again.Therefore, using CVD manufacture , it is necessary to be cleaned before excessively excess carburizing is carried out during CNT.

The present inventor etc. has found, carbon in the carbon of furnace wall and furnace interior part etc. dirt is attached to, is taken off due to excess carburizing In the case that carbon in the carbon dirt for falling or peeling off reacts with water, mainly there is above-mentioned (a) reaction, in carburizing to furnace wall and furnace interior In the case that the carbon of part reacts with water, mainly there is above-mentioned (b) reaction.Further, the present inventor etc. has found occurring excessively to ooze Under state (usual carburizing state) before carbon, because carbon and the water in clean gas of carburizing to furnace wall and furnace interior part occur The ratio of reaction is high, therefore is substantially carried out above-mentioned (b) reaction, and the yield of carbon dioxide increases compared with carbon monoxide；And, In the state of it there occurs excess carburizing, because the water in the carbon and clean gas in the carbon dirt that comes off or peel off reacts Ratio is high, therefore is substantially carried out above-mentioned (a) reaction, and the yield of carbon monoxide increases compared with carbon dioxide.That is, the present inventor Deng finding, [CO]/[CO can be based on₂] value judge whether furnace wall and furnace interior part there occurs excess carburizing.

Therefore, in cleaning process, to carrying out cleaning so that meeting in above-mentioned growth furnace：

0 ＜ ([CO]/[CO₂])≤10···(2)。

By carrying out cleaning process so that meeting such scope, can be excessive in the excess carburizing of furnace wall and furnace interior part Effectively cleaned before carrying out.And then, as a result, the generation of excess carburizing can be prevented.

In addition, in cleaning process, more preferably to being cleaned so as to reach 0 ＜ ([CO]/[CO in growth furnace 13₂])≤ 3 scope, further preferably to being cleaned so as to reach 0 ＜ ([CO]/[CO in growth furnace 13₂])≤1 scope.

So, in cleaning process, by the concentration based on the hydrogen in growth furnace 13, carbon dioxide and carbon monoxide Cleaned, just right cleaning can be carried out.Thus, it is possible to the long lifetime of growth furnace and the high efficiency of cleaning are realized, And then the yield of CNT manufactures can be improved.

It should be noted that in cleaning process, in order to carry out cleaning the hydrogen, the carbon dioxide and that cause in growth furnace 13 The concentration of carbonoxide meets the scope of above-mentioned formula (1) or the scope of above-mentioned formula (1) and (2), can suitably adjust clean gas Quantity delivered, clean gas in the clean conditions such as amount of moisture, temperature, cleaning time in the growth furnace 13 in cleaning process. Because the concentration of the hydrogen in growth furnace 13, carbon dioxide and carbon monoxide is according to state (the attachment shape of carbon dirt in growth furnace 13 State, carburizing state etc.) it is and different, therefore, suitably adjust clean conditions, to reach above range in the way of cleaned.

For example, the amount of moisture in clean gas in terms of volumetric concentration can as 1000ppm more than and below 100000ppm, More preferably more than 2000ppm and below 50000ppm, more preferably more than 4000ppm and below 30000ppm.Pass through Make the amount of moisture in clean gas in such scope, can suitably remove the carbon dirt for being attached to furnace wall and furnace interior part etc., The manufacture of high-quality CNT can be immediately realized after the cleaning.

In addition, the temperature in growth furnace 13 for example in cleaning process can be more than 600 DEG C and less than 1100 DEG C, more Preferably more than 700 DEG C and less than 1000 DEG C, more preferably more than 750 DEG C and less than 900 DEG C.In by making cleaning process Growth furnace 13 in temperature in such scope, can in a short time remove the carbon for being attached to furnace wall and furnace interior part etc. Dirt.Further, since the temperature difference in cleaning process and growth operation in growth furnace 13 is small, thus be carried out continuously growth operation and In the case of cleaning process, the time to growth operation starts after cleaning process can be shortened, can be good with productivity The CNT of ground manufacture high-quality.

Further, for example the cleaning time in cleaning process can be more than 1 hour and less than 100 hours, more preferably 3 Hour more than and less than 50 hours, more preferably more than 5 hours and less than 20 hours.By making cleaning time such Scope, can in a short time effectively to being cleaned in growth furnace 13.

In the manufacture method of CNT of the invention, separately carry out growing operation and cleaning process.Cleaning process Can be alternately carried out with growth operation, can also be after growth operation be repeated to a certain extent, when appropriate Quarter carries out cleaning process.Quality alternatively, it is also possible to the CNT when operation grow to growing is evaluated, and is being evaluated Quality be unsatisfactory for given condition in the case of carry out cleaning process.The quality of CNT for example can be according to above-mentioned G/D ratios etc. Evaluated.

But, due to needing that cleaning process is carried out before exceedingly carrying out excess carburizing in the growth furnace 13, therefore will be More than 0 ＜ [CO]/[CO₂Start cleaning before]≤10.That is, in advance to that can make when which kind of is grown under conditions of operation [CO]/[CO₂] held no more than 10, in [CO]/[CO₂] no more than 10 when start cleaning.Or, every to timing Between to the gas comprising water is imported in the growth furnace 13 of the state for not sending into base material, make its with growth furnace 13 in substance reaction, And the eudiometry in growth furnace 13 is carried out, in [CO]/[CO₂] no more than 10 when start cleaning.

So, it is possible to use [CO]/[CO₂] value as cleaning start index.As long as in addition, 0 ＜ [CO]/ [CO₂In the range of]≤10, you can be judged as excess carburizing.

So, it is described " in cleaning process, to cause to meet 0 ＜ [CO]/[CO to carrying out cleaning in above-mentioned growth furnace₂]≤ 10 ", the condition for being also included within opposite operation long when starting cleaning is adjusted, causes [CO]/[CO₂] below 10.

Further, since need to terminate cleaning before it there is the oxidation in growth furnace, therefore, departing from 0.7≤{ (2 [CO₂]+[CO])/[H₂] terminate cleaning before≤1.3 scope.I.e., it is possible to by (2 [CO₂]+[CO])/[H₂] value as clear The index of clean end.In other words, if (2 [CO₂]+[CO])/[H₂] within the range, then can be cleaned until carbon dirt reaches To desired degree.

In cleaning process, it is also possible to be further measured the (2 [CO in growth furnace 13₂]+[CO])/[H₂] monitoring. By monitoring (2 [CO in cleaning₂]+[CO])/[H₂] value, can suitably hold the state of oxidation in growth furnace 13 so that The opportunity that cleaning terminates can suitably be judged.Specifically, can be by monitoring 2 [CO₂]+[CO])/[H₂] value through when The trend of change, in (2 [CO₂]+[CO])/[H₂] value reach less than 0.7 or more than 1.3 before terminate cleaning process.

In addition, in cleaning process, can adjust cleaning process implementation condition (for example, amount of moisture in clean gas, It is more than any one in clean gas flow and growth in-furnace temperature etc.) so that (2 [CO in growth furnace 13₂]+[CO])/ [H₂] value be not less than 0.7 or more than 1.3 surpassing.

Further, in cleaning process, it is also possible to be further measured [CO]/[CO in above-mentioned growth furnace₂] prison Survey.By monitoring [CO]/[CO in cleaning₂] value, the state of the carburizing in growth furnace 13 can be held.

In addition, in cleaning process, if [CO]/[CO that cleaning is determined when just starting₂] already exceed 10, then by adjusting Whole clean conditions can more efficiently prevent from the generation of excess carburizing to obtain high cleaning effect.

Specifically, in cleaning process, [CO]/[CO can be monitored with side₂] value come hold the carbon in growth furnace 13 dirt And the removing state of carburizing, the implementation condition of side adjustment cleaning process is (for example, amount of moisture, clean gas stream in clean gas Between more than any one in amount and growth in-furnace temperature or at the beginning of cleaning process, end time etc.), cause [CO]/ [CO₂] value be no more than 10.

[CNT manufacture devices]

Next, being illustrated to the CNT manufacture devices for possessing growing element with reference to Fig. 2.Fig. 2 is to show of the invention one The schematic diagram of other examples of the manufacture device used in the manufacture method that implementation method is related to.CNT manufacture devices 100 be for Realize the device of the manufacture method of CNT.

CNT manufacture devices 100 possess：Entrance purification portion 1, formation unit 2, gas are mixed into anti-locking mechanism 101~103, life Unit long 3, cooling unit 4, outlet purification portion 5, supply unit 6 and connecting portion 7~9.

Form unit 2 to possess to form stove 2a, growing element 3 possesses growth furnace 3a, cooling unit 4 possesses cooling stove 4a.Shape Into stove 2a, growth furnace 3a and each furnace inner space for cooling down stove 4a in the shape of the formation connection spatially by connecting portion 7~9 State.

(entrance purification portion)

The entrance of CNT manufacture devices 100 is provided with entrance purification portion 1.Entrance purification portion 1 is for preventing extraneous air The set of device in device stove is mixed into from the entrance of base material 20.Entrance purification portion 1 has using purification gas to being transported to dress The surrounding environment of the base material 20 in putting enters the function of line replacement.It should be noted that base material 20 has and the base shown in above-mentioned Fig. 1 The identical of material 12 is constituted.

Entrance purification portion 1 is used purification gas from the air curtain structure for being in up and down the injection of shape spray piece.Thus it is outer to prevent The air in portion is mixed into CNT manufacture devices 100 from entrance.Entrance purification portion 1 for example can be by the stove for keeping purification gas Or chamber and constituted for spraying the ejection section etc. of purification gas.

Used as purification gas, preferably inactive gas especially goes out from viewpoints such as security, cost and purification property Hair, purification gas are preferably nitrogen.

As in this embodiment, supply unit 6 is the entrance of situation of conveyer belt mode etc., base material 20 to open all the time In the case of mouthful, entrance purification portion 1 is preferably above-mentioned air curtain structure.By using this composition, the air of outside can be prevented The inside of CNT manufacture devices 100 is mixed into from the entrance of base material 20.

(formation unit)

It is the set of device for implementing formation process to form unit 2.Forming unit 2 has the table that will be formed in base material 20 The surrounding environment of the catalyst in face is adjusted to reducing gas environment, and at least one of catalyst and reducing gas are carried out The function of heating.

Unit 2 is formed to include：For keeping the formation stove 2a of reducing gas, for spraying reducing gas to being formed in stove 2a Reducing gas ejection section 2b, for the heater 2c that is heated at least one of catalyst and reducing gas and Hood 2d for the gas exhaust in stove 2a will to be formed.

The shower nozzle for possessing multiple jets can also be used in reducing gas ejection section 2b.Reducing gas ejection section 2b The catalyst being arranged in face of base material 20 forms the position in face.The position that faces refers to, the jet axis of each jet with Angle formed by the normal of base material 20 is 0 ° less than 90 ° of position.That is, it is arranged so that from reducing gas ejection section 2b's The direction of the air-flow that jet sprays is substantially orthogonal with base material 20.

If reducing gas can be uniformly dispersed in base material 20 by reducing gas ejection section 2b using such shower nozzle On, being capable of effectively reducing catalyst.As a result, the uniformity of the CNT grown on base material 20 can be improved, and also can Cut down the consumption of reducing gas.

As heater 2c, as long as can be heated at least one of catalyst and reducing gas, have no Limit, for example, can enumerate：Resistance heater, infrared heater, induction heater etc..As the temperature of heating, It is preferred that in 400 DEG C~1100 DEG C of scope.

Reducing gas is typically the gaseous gas with least one of following effects：By catalyst reduction, promote The micronized (be changing into and be suitable to the state of CNT growth) of catalyst and the activity of raising catalyst.As reducing gas, can To use such as hydrogen, ammonia, vapor and their mixed gas.Alternatively, it is also possible to using by these gases and helium, The mixed gas that the inactive gas such as argon gas, nitrogen are mixed.Reducing gas is generally used in formation process, but can also be fitted Locality is for growing operation.

Formation process refers to that the surrounding environment of the catalyst that will be carried on base material 20 is adjusted to reducing gas environment and right The operation that catalyst and/or reducing gas are heated.By the operation, at least one of following effects can be shown： By catalyst reduction, promote the micronized (becoming suitable for the state of CNT growth) of catalyst and improve the activity of catalyst.

The temperature of catalyst and/or reducing gas in formation process is preferably more than 400 DEG C and less than 1100 DEG C.Separately Outward, the time of formation process be preferably more than 3 minutes and less than 30 minutes, more preferably more than 3 minutes and less than 8 minutes.Such as The time of fruit formation process in the scope, then can prevent the multilayer carbon in coarsening, the Developing restraint operation of catalyst particles The generation of nanotube.

For example, in the case where iron is used as catalyst, iron hydroxide film or sull can be formed, while or Person is reduced and micronized behind, so as to form the particulate of iron.And then, prevent the material of layer for aluminum oxide in carburizing and In the case that catalyst metals are iron, iron catalyst carries out micronized through reduction, so as to form substantial amounts of on alumina layer The iron granules of nano-grade size.Thus by catalyst preparation into the catalyst for being suitable to the production of CNT.

(growing element)

Growing element 3 is the set of device for implementation growth operation, including remains the environment around base material 20 The stove of unstrpped gas environment is growth furnace 3a, the unstrpped gas ejection section 200 for being injected in unstrpped gas on base material 20, use In the heater 3b heated at least one of catalyst and unstrpped gas and for by the gas in growth furnace 3a The hood 3c of exhaust.Additionally, growing element 3 can also have the activation of catalyst material for supplying activation of catalyst material Ejection section (not shown) and the clean gas ejection section (not shown) for supplying clean gas.It should be noted that raw material Gas injection portion 200 can be with simultaneous for activation of catalyst surge portion and/or clean gas ejection section.

Growth furnace 3a is the stove for grow operation, is for the surrounding environment by making the catalyst on base material 20 Heated as unstrpped gas environment and at least one of catalyst and unstrpped gas so that CNT orientation aggregations The stove grown on base material 20.

In operation is grown, preferably original is sprayed to the base material 20 moved in growth furnace 3a from unstrpped gas ejection section 200 Material gas.

Preferred feedstock gas injection portion 200 and hood 3c respectively have more than at least one, and are sprayed from whole unstrpped gas The total gas couette and the total gas couette from whole hood 3c exhausts for penetrating the injection of portion 200 are basic equivalent or equivalent.By This, can prevent unstrpped gas from flowing out to the gas outside growth furnace 3a, and outside growth furnace 3a and flow into growth furnace 3a.

Used as heater 3b, scope that preferably can be by catalyst and/or unstrpped gas at 400 DEG C~1100 DEG C is added The heater of heat, can enumerate for example：Resistance heater, infrared heater, induction heater etc..

When CNT orientation aggregations is grown on base material 20 in growth furnace 3a, the pressure in growth furnace 3a is preferably 10²More than Pa and 10⁷Pa (100 atmospheric pressure) below, more preferably 10⁴More than Pa and 3 × 10⁵Pa (3 atmospheric pressure) with Under.

In addition, in growth furnace 3a, alloing the reaction temperature of CNT growth considering the species of catalyst and unstrpped gas Suitably determine with the case of concentration and reaction pressure etc., but be preferably set to so that being lost as catalyst for excluding The effect of the activation of catalyst material of the accessory substance of living the reason for is able to the temperature range for fully demonstrating.That is, as most preferred Temperature range, can remove the temperature of the accessory substances such as amorphous carbon, graphite as lower limit, as master with activation of catalyst material The temperature that the CNT of product will not be aoxidized by activation of catalyst material is higher limit.

In operation is grown, can be by making to have reached the state that can manufacture CNT using such as formation process etc. Making the surrounding environment of the catalyst of CNT growth turns into unstrpped gas environment and at least one of catalyst and unstrpped gas Heated, thus made CNT growth.The detailed description for growing operation is as described above.

The detailed description of cleaning process is as described above.It should be noted that it is preferred that grow operation after cleaning process it It is preceding including stopping being sent to base material 20 in growth furnace 3a and stopping the operation to base feed gas in growth furnace 3a. In the operation, for example, stopping being sent to base material 20 in growth furnace 3a first, and the base in growth furnace 3a can be will be present in After material 20 takes out of outside growth furnace 3a completely, stop the supply of unstrpped gas.Additionally, it is preferred that growing work after cleaning process Include starting that base material 20 is sent in growth furnace 3a and started the operation to base feed gas in growth furnace 3a before sequence.

(supply unit)

Supply unit 6 refers in order to multiple base materials 20 are continually fed into a necessary suit in CNT manufacture devices 100 Put.Supply unit 6 possesses guipure 6a and band drive division 6b.Base material 20 passes through supply unit 6 in each furnace inner space according to formation Unit 2, growing element 3 and cooling unit 4 it is sequentially supplied.

Supply unit 6 is the device of conveyor type, from space in formation stove 2a by space in growth furnace 3a to cooling stove Space feed surface is formed with the base material 20 of catalyst in 4a.Supply unit 6 conveys base material 20, the guipure using such as guipure 6a 6a is to be used being driven with drive division 6b for the motor with decelerator etc..In addition, in CNT manufacture devices 100, being formed In stove 2a in space and growth furnace 3a between space and in growth furnace 3a in space and cooling stove 4a between space by connection Realize connection spatially in portion 8 and 9.Thus, the guipure 6a for being placed with base material 20 can pass through between each stove.

It should be noted that the situation of the device of CNT being manufactured for continous way in CNT manufacture devices 100, possessing conveying In the case of unit, its specific composition is not limited to above-mentioned composition, for example, supply unit can also be the machine in multi-chamber mode Tool arm, mechanical arm driving device etc..

(connecting portion)

Connecting portion 7~9 refers to from unit to unit for the furnace inner space of each unit spatially to be connected, in base material 20 Base material 20 is prevented to be externally exposed the set of device of gas during conveying.As connecting portion 7~9, can enumerate for example：By base material week Collarette border and extraneous gas are isolated, and enable stove from unit to unit or chamber that base material 20 passes through from etc..

Entrance purification portion 1 and formation unit 2 realize connection spatially by connecting portion 7.Gas is configured with connecting portion 7 It is mixed into anti-locking mechanism 101, purification gas of the discharge in the injection of entrance purification portion 1 and the reduction from reducing gas ejection section 2b injections The mixed gas of gas.It is mixed into space and reducing gas in formation stove 2a this prevents purification gas and is mixed into entrance The side of purification portion 1.

Formation unit 2 and growing element 3 realize connection spatially by connecting portion 8.Gas is configured with connecting portion 8 to mix Enter anti-locking mechanism 102, discharge forms the unstrpped gas and catalyst in space in the reducing gas in space and growth furnace 3a in stove 2a Activating substance.Space and reducing gas to formation stove 2a are mixed into this prevents unstrpped gas or activation of catalyst material It is mixed into space in growth furnace 3a.

Growing element 3 and cooling unit 4 realize connection spatially by connecting portion 9.Gas is configured with connecting portion 9 to mix Enter anti-locking mechanism 103, space in the unstrpped gas and activation of catalyst material and cooling stove 4a in space in discharge growth furnace 3a The mixed gas of inactive gas.This prevents unstrpped gas or activation of catalyst material be mixed into space in cooling stove 4a, And inactive gas is mixed into space in growth furnace 3a.

It should be noted that CNT manufacture devices 100 can be also further equipped between growing element 3 and cooling unit 4 The heating arrangements that connecting portion 9 is heated.Here, growth furnace 3a near exit temperature reduction when, unstrpped gas point Solution thing turns into amorphous carbon, is likely to accumulate in the leading section of CNT.It is thereby possible to cause the CNT vertically grown from base material Leading section (top) G/D ratios less than root (bottom) G/D ratios.

But, heated by the connecting portion 9 between growing element 3 and cooling unit 4, the G/ of leading section can be made D than the G/D with root than difference diminish.Thereby, it is possible to obtain the CNT of stay in grade.

As the concrete form of the heating arrangements heated to connecting portion 9, for example, it may be in the He of growing element 3 Gas between cooling unit 4 is mixed into the mechanism that the sealing gas of the ejection of anti-locking mechanism 103 are heated.By to sealing gas Heated, can be realized to the outlet of growth furnace 3a and its neighbouring heating.

(gas is mixed into anti-locking mechanism)

It is the set of device for implementing function such as that gas is mixed into anti-locking mechanism 101~103：Prevent in the stove of each unit Gas present in space is mutually mixed into.Gas is mixed into anti-locking mechanism 101~103 and is arranged at makes the furnace inner space of each unit mutual The connecting portion 7~9 for spatially connecting.Gas is mixed into anti-locking mechanism 101~103 and possesses the respective blanket gas of at least more than one Body ejection section 101b~103b and exhaust portion 101a~103a, sealing gas ejection section 101b~103b is along the base material 20 in each stove Entrance and the opening surface of outlet spray sealing gas, exhaust portion 101a~103a mainly aspirate sprayed sealing gas (and Gas near other) so that its gas that do not enter in each stove and will be aspirated is discharged to outside device.

Sealing gas are sprayed along the opening surface of stove, it is possible thereby to sealing gas is blocked the gateway of stove, so as to prevent Gas outside stove is mixed into stove.In addition, being discharged to outside device by by sealing gas, it is prevented from sealing gas and is mixed into stove.

Sealing gas are preferably inactive gas, particularly from the viewpoints such as security, cost, preferably nitrogen.Make It is 101b~103b and 1 configuration of exhaust portion 101a~103a of 1 sealing gas ejection section, can be sprayed with 1 sealing gas Penetrate portion and adjacently configure 1 exhaust portion, it is also possible to according to clipping guipure 6a and the mode relative with sealing gas ejection section is matched somebody with somebody Put exhaust portion.It should be noted that preferably, so that gas is mixed into being monolithically fabricated for anti-locking mechanism 101~103 and turns into stove The mode of symmetrical structure configures sealing gas ejection section 101b~103b and exhaust portion 101a~103a on length direction.

For example, 2 sealing gas ejection sections can be configured at 1 two ends of exhaust portion, and along stove centered on exhaust portion Length direction forms symmetrical structure.Additionally, it is preferred that from all gas flow of sealing gas ejection section 101b~103b injection and from The all gas flow of exhaust portion 101a~103a discharges is roughly the same amount.This prevents being mixed into from clipping gas The gas in the space of the both sides of anti-locking mechanism 101~103 is mutually mixed into, and also is prevented from sealing gas and flows out to both sides Space.The two ends that anti-locking mechanism 101~103 is arranged on growth furnace 3a are mixed into by by such gas, sealing is prevented from The air-flow of the gas in the air-flow and growth furnace 3a of gas is interfered.In addition, flowing into growth furnace 3a prevented also from sealing gas The disorder that gas that is interior and causing flows.Thereby, it is possible to realize being suitable to the device of the continuous manufacture of CNT.

In addition, the degree that the gas prevented as anti-locking mechanism 101~103 is mixed into by gas is mixed into, preferably not Hinder the degree of the manufacture of CNT orientation aggregations.It is particularly preferred to gas is mixed into anti-locking mechanism and have and will form going back in stove 2a Carbon atom number concentration in raw-gas environment is maintained at 5 × 10²²Individual/m³Below, more preferably it is maintained at 1 × 10²²Individual/m³Below Function.

Each capacity Q of the multiple exhaust portion 101a~103a being had cannot determine independently of each other.Need according to dress Overall gas delivery volume (reducing gas flow, raw material gas flow and cooling gas flow etc.) is put to be adjusted.But, Can be shown below for meeting the necessary condition for preventing that gas is mixed into.

Q≥4DS/L

Here, D is intended to prevent the diffusion coefficient of the gas being mixed into, and S is the sectional area on the border for preventing gas to be mixed into, and L is The length (furnace superintendent direction) of exhaust portion.Mode according to the conditional and the overall supply and discharge gas balance of holding meanss is met sets respectively The capacity of exhaust portion 101a~103a.

If unstrpped gas is mixed into form space in stove 2a, harmful effect can be produced to the growth of CNT.It is therefore preferable that Anti- locking mechanism 101 and 102 is mixed into by gas to prevent from unstrpped gas to be mixed into being formed in stove 2a, so that formed in stove 2a also Carbon atom number concentration in raw-gas environment is maintained at 5 × 10²²Individual/m³Below, more preferably it is maintained at 1 × 10²²Individual/m³With Under.Here, carbon atom number concentration can be calculated as follows：In for reducing gas environment each gaseous species (i=1, 2nd), concentration (volume ppm) is set to D₁、D₂, by the density (g/m under standard state³) it is set to ρ₁、 ρ₂, molecular weight is set to M₁、M₂, the carbon number included in a gas molecule is set to C₁、C₂···、 Avogadro's number is set to N_A, calculated using following mathematical expressions (2).

[mathematical expression 2]

5 × 10 are maintained at by the way that the carbon atom number concentration in the reducing gas environment in stove 2a will be formed²²Individual/m³With Under, can well keep the manufacture and quality of CNT.That is, 5 × 10 are maintained at by by carbon atom number concentration²²Individual/m³With Under, in formation process, reducing catalyst can be well given play to, promote the micronized of catalyst and improve catalyst Activity and other effects, and then, can well keep growing the manufacture and quality of the CNT in operation.

It should be noted that being mixed into anti-locking mechanism 101~103 as gas, however it is not limited to the structure in present embodiment, Can also in the time for example beyond the time that base material 20 is moved from unit to unit, mechanically block each unit in space On connection gate-valve device.Alternatively, it is also possible to be that each unit connection spatially is blocked by spraying inactive gas Air curtain device.

It is mixed into be prevented securely from gas, preferably gate-valve device and/or air curtain device are combined with exhaust apparatus makes With.In addition, being conveyed so as to effectively carry out continuous CNT growth from by between the unit-unit for carrying out base material incessantly From the viewpoint of viewpoint and simplified manufacture device, exhaust apparatus is more preferably used alone.

(cooling unit)

Cooling unit 4 refers to for realizing refrigerating work procedure, the base material 20 being used for having grown CNT are cooled down one Covering device.Cooling unit 4 has the function that CNT and base material 20 after opposite operation long are cooled down.

Cooling unit 4 is the composition for being combined with water-cooling pattern and air cooling mode, and it includes：For keeping inactive gas Cool down stove 4a, cool down stove 4a to the cooling gas ejection section 4b of space injection inactive gas in cooling stove 4a and according to surrounding The water-cooled condenser pipe 4c that the mode in interior space is configured.It should be noted that cooling unit 4 can also be merely the structure of water-cooling pattern Into or the only composition of air cooling mode.

Cooled down by using cooling unit 4, can be prevented from growing the oxygen of CNT, catalyst and base material 20 after operation Change.

Refrigerating work procedure refers to the work cooled down to CNT, catalyst and base material in inactive gas after operation is grown Sequence.Because the CNT after growth operation, catalyst and base material are in the condition of high temperature, therefore may being placed in when oxygen is deposited in the environment Can aoxidize.In order to prevent the problem, in refrigerating work procedure, CNT, catalyst and base are cooled down in inactive gas environment Material.Temperature in refrigerating work procedure is less than 400 DEG C, more preferably less than 200 DEG C.

(outlet purification portion)

The outlet of CNT manufacture devices 100 is provided with the structure outlet purification portion 5 roughly the same with entrance purification portion 1.Go out Mouth purification portion 5 refers to the suit for preventing extraneous air that the inside of CNT manufacture devices 100 is mixed into from the outlet of base material 20 Put.Outlet purification portion 5 has makes function of the surrounding environment of base material 20 as purge gas environment.

Outlet purification portion 5 from purification gas are sprayed in shape spray up and down by preventing extraneous air to be mixed into cold from outlet But in stove 4a.It should be noted that outlet purification portion 5 can also by for keep purge gas environment stove or chamber and Ejection section etc. for spraying purification gas is constituted.

As purification gas, preferably inactive gas, particularly from from the aspect of security, cost and purification property etc., It is preferred that purification gas are nitrogen.

It is in the case of being open all the time, preferably to go out in the outlet of situation that supply unit 6 is conveyer belt mode etc., base material 20 Mouth purification portion 5 is above-mentioned air curtain structure.By using the structure, the outlet for being prevented from extraneous gas from base material 20 is mixed into The inside of CNT manufacture devices 100.

Device feature in reducing gas or unstrpped gas be to be formed unit 2, growing element 3, supply unit 6, Gas is mixed into the section components of anti-locking mechanism 101~103 and connecting portion 7~9.Specifically, as exposed to reducing gas or Device feature in unstrpped gas, can enumerate to form stove 2a, reducing gas ejection section 2b, growth furnace 3a, unstrpped gas injection The devices such as the stove of portion 200, guipure 6a, exhaust portion 101a~103a, sealing gas ejection section 101b~103b and connecting portion 7~9 Part.

As the material of the device feature in reducing gas or unstrpped gas, resistant to elevated temperatures material can be enumerated, For example from the aspect of quartz, heat-stable ceramic, metal etc., precision, the free degree and cost from processing etc., preferred metal.As gold Category, can enumerate heat-resisting alloy etc..As heat-resisting alloy, can enumerate：Heat resisting steel, stainless steel and nickel-base alloy etc..Based on Fe Composition, other alloy concentrations are commonly known as heat resisting steel in the steel of below 50 mass %.In addition, with Fe as principal component, other conjunction The steel of Cr of the gold concentration in below 50 mass % and containing more than about 12 mass % is commonly known as stainless steel.In addition, as nickel Based alloy, can enumerate the alloy that Mo, Cr and Fe etc. are with the addition of in Ni.Specifically, SUS310, Inconel 600, Inconel 601, Inconel 625, Incoloy 800, MC alloys and the alloys of Haynes 230 etc. are strong from heat resistance, machinery From the aspect of degree, chemical stability and low cost etc. preferably.

Be made up of metal use part in stove inwall and/or stove when, preferably make material for heat-resisting alloy and to its surface Melt aluminizing and process or be processed by shot blasting so that the arithmetic average roughness on its surface reaches Ra≤2 μm.By the structure Into, can reduce in high-carbon environment grow CNT when be attached on wall etc. carbon dirt.Thereby, it is possible to prevent the manufacture of CNT Reduction and quality deterioration, so it is preferred that.

It refers to be immersed in bath of molten aluminum by that will be plated material to melt treatment of aluminizing, so as to be plated material Surface forms the treatment of aluminum or aluminum alloy layer.The one of processing method is for example lower shown.Surface to being plated material (mother metal) is entered After row washing (pretreatment), it is immersed in about 700 DEG C of bath of molten aluminum, thus causes molten aluminum to the diffusion on mother metal surface, generation The alloy of mother metal and aluminium, so as to make aluminium be attached to its alloy-layer when being pulled out from bath.Further, it is also possible to behind to top layer Alumina layer and aluminium lamination carry out low temperature heat diffusion treatment, enter to exercise the treatment that its lower Fe-Al alloy layer is exposed.

As for making heat-resisting alloy reach the polishing method of the arithmetic average roughness of Ra≤2 μm, can enumerate To polish the mechanical polishing for representative, the chemical polishing using medicine, circulating current is while the electricity being polished in the electrolytic solution Solution polishing and by mechanical polishing and electrobrightening combine combined electrolysis polishing etc..

The definition of arithmetic average roughness Ra is with reference to " JIS B0601:2001”.

As described above, for manufacture method of the present invention, in CNT manufacture devices 100, utilizing supply unit 6 continuously transport surface while have base material 20 of catalyst, the base material 20 passed sequentially through entrance purification portion 1, formed single Unit 2, growing element 3, cooling unit 4 and outlet purification portion 5.Therebetween, in the reducing gas environment for forming unit 2, catalyst It is reduced, in the unstrpped gas environment of growing element 3, in the superficial growth CNT of base material, is cooled in cooling unit 4.

More than, the preferred embodiment of the present invention is illustrated, but the invention is not restricted to the implementation method, in its master Various modifications and change can be carried out in the range of purport.

For example, by suitably setting unstrpped gas, the reaction condition such as heating-up temperature, can optionally manufacture single wall or Many wall CNT, can also be such that both are manufactured with being mixed.

In addition, in the present embodiment, to being entered in substrate surface using the other film formation device different from manufacture device The situation of the formation of row catalyst is illustrated.But it is also possible to set catalyst film forming list in the upstream side for forming unit 2 Unit, with make base material before forming unit 2 by catalyst into being constituted manufacture device by way of film unit.

In addition, in the present embodiment, each list is set according to the order for forming unit 2, growing element 3 and cooling unit 4 Unit, each furnace inner space is spatially connected by connecting portion 7~9.But multiple also can be somewhere set up to be used to realize removing form work The unit of other operations beyond sequence, growth operation and refrigerating work procedure, each unit is spatially connected by connecting portion 7~9 Furnace inner space.

In addition, in the present embodiment, for the configuration of each unit for forming unit 2, growing element 3 and cooling unit 4 For the situation of linear configuration is illustrated.But, the configuration of each unit is not limited to this, for example, can also be cyclic ligand Put.

Additionally, it is so far main to the preferred mode for being continuously manufactured by CNT, be respectively provided with to form unit 2 And growing element 3 and be illustrated the mode that base material 20 is continually fed into unit, but the CNT systems used in the present invention Make device and be not limited to such mode.

The invention is not restricted to above-mentioned each implementation method, various changes can be within the scope of the claims carried out, will be Implementation method obtained from disclosed technological means is combined respectively in different embodiments is also contained in technology of the invention In the range of.

Embodiment

For one embodiment of the invention, it is described as follows based on Fig. 3~Fig. 9.It should be noted that the invention is not restricted to Under embodiment.

Here, the growth furnace used in following reference example 1 and 2 is made up of quartz, the growth furnace used in embodiment It is to be made up of through melting the material for the treatment of of aluminizing the surface of SUS310.

[reference example 1：Through the cleaning of the growth furnace sample after usual carburizing]

In batch-type growth furnace as shown in Figure 1, implement to clean for sample strip (4.5cm × 13cm × 0.25mm), Determine the concentration of each gas (hydrogen, carbon monoxide and carbon dioxide) in now furnace gas.It should be noted that as real The sample strip of cleaning is applied, materials described below has been used：It is that the surface of SUS310 is aluminized and carried out plating by melting to mother metal Material piece, in following CNT manufacture devices, the manufacturing condition identical condition of aggregation is being orientated with CNT as follows (830 DEG C of in-furnace temperature, unstrpped gas：160sccm is (relatively wet for nitrogen 16040sccm, ethene 1800sccm, containing water vapor nitrogen Degree 22.3%)) under carry out 60 hours sample strips of carburizing.

In the cleaning implemented to sample strip, clean conditions are set as shown in Table 1 below.

[table 1]

The relation that automatically cleaning starts between the moisture concentration after 5 minutes and each gas concentration is as shown in Figure 3.Shown in Fig. 3 Each gas concentration (the gas concentration as described in Table 2 shown in coordinate diagram：Volume ppm).

[table 2]

H₂O	CO₂	CO	H₂	(2[CO₂]+[CO])/[H₂]	[CO]/[CO₂]
						5534	196	0	375	1.04	0.00
7992	233	22	449	1.08	0.09
						11153	246	11	467	1.07	0.04

The relation that automatically cleaning starts between the in-furnace temperature after 5 minutes and each gas concentration is as shown in Figure 4.Shown in Fig. 4 Each gas concentration (the temperature as described in Table 3 shown in coordinate diagram：DEG C, gas concentration：Volume ppm).

[table 3]

Temperature	CO₂	CO	H₂	(2[CO₂]+[CO])/[H₂]	[CO]/[CO₂]
						800	117	0	223	1.05	0.00
850	246	11	467	1.07	0.04
						900	544	69	1075	1.08	0.13
950	921	265	2041	1.03	0.29

As shown in Fig. 3 and table 2, in the range of the volume ppm of moisture concentration 5000~12000, following tendencies are observed： Hydrogen and carbon dioxide are produced relatively largely, and proportional between its concentration and moisture concentration.This represents moisture concentration and cleaning Speed is proportional.On the other hand, the yield of carbon monoxide is very micro.

As shown in Fig. 4 and table 3, in the range of 800~950 DEG C of temperature, following tendencies are observed：Hydrogen and carbon dioxide Produce relatively largely, and itself and temperature proportional.This represents that temperature and cleaning speed are proportional.In addition, with regard to carbon monoxide Speech, observed with the increased tendency in temperature proportional ground, but yield is still for micro.

Either on moisture concentration or temperature, shown in gamut：(2[CO₂]+[CO])/[H₂] value 1 is remained essentially as, can monitor to be aoxidized substantially in growth furnace in cleaning.Show in addition：[CO]/[CO₂] Value is maintained at less than 1 in gamut, in the case of being cleaned in the growth furnace after to carburizing occurs, no matter cleans How is condition, and the yield of carbon monoxide is less than the yield of carbon dioxide.

[reference example 2：From the cleaning that there occurs carbon that the growth furnace of excess carburizing comes off dirt]

In the batch-type growth furnace shown in Fig. 1, implement cleaning for carbon dirt sample (0.45g), and determine now stove The concentration of each gas (hydrogen, carbon monoxide and carbon dioxide) in interior gas.Carbon dirt sample is from the sample for having made reference example 1 The sample of collection in CNT manufacture devices after piece, the growth furnace is that the surface of SUS310 is carried out to melt treatment of aluminizing Stove.Further, carbon dirt sample includes the metal ingredient from furnace wall.

In the cleaning implemented to carbon dirt sample, clean conditions are set as described in Table 4.

[table 4]

The relation that automatically cleaning starts between the moisture concentration after 5 minutes and each gas concentration is as shown in Figure 5.Shown in Fig. 5 Each gas concentration (the gas concentration as described in Table 5 shown in coordinate diagram：Volume ppm).

[table 5]

H₂O	CO₂CO	H₂	(2[CO₂]+[CO])/[H₂]	[CO]/[CO₂]
					5577	99841	925	1.12	8.54
8212	2522477	2558	1.17	9.83
					10993	2953065	3111	1.18	10.38

The relation that automatically cleaning starts between the in-furnace temperature after 5 minutes and each gas concentration is as shown in Figure 6.Shown in Fig. 6 Each gas concentration (the temperature as described in Table 6 shown in coordinate diagram：DEG C, gas concentration：Volume ppm).

[table 6]

Temperature	CO₂	CO	H₂	(2[CO₂]+[CO])/[H₂]	[CO]/[CO₂]
						750	78	5392	4397	1.26	68.95
800	51	6170	5205	1.20	121.6
						850	295	3065	3111	1.18	10.4
900	430	1807	2354	1.13	4.2
						950	718	1845	2966	1.11	2.6

As shown in Fig. 5 and table 5, in the range of the volume ppm of moisture concentration 5000~12000, following tendencies are observed： Hydrogen and carbon monoxide are produced relatively largely, and proportional between its concentration and moisture concentration.This represents moisture concentration and cleaning Speed is proportional.On the other hand, the yield of carbon dioxide is more micro.

As shown in Fig. 6 and table 6, in the range of 750~950 DEG C of temperature, following tendencies are observed：Hydrogen and carbon monoxide Produce relatively largely, and there is extreme value near 800 DEG C.This represents that cleaning speed becomes most fast near 800 DEG C.In addition, Carbon dioxide and the increased tendency in temperature proportional ground are observed, but yield is more micro.

Either on moisture concentration or temperature, it is shown as in gamut：(2[CO₂]+[CO])/[H₂] value 1 is remained essentially as, can monitor that the metal ingredient included in carbon dirt in cleaning is aoxidized substantially.Show in addition： [CO]/[CO₂] value be maintained at more than 1 in gamut, cleaning of carbon dirt in the case of, regardless of clean conditions, The yield of carbon monoxide is more than the yield of carbon dioxide.

In reference example 1 and 2, regardless of clean conditions, the concentration ratio phase of carbon monoxide and carbon dioxide is shown Should be changed in the carburizing situation in growth furnace.Will not cause that the degree that carbon dirt is peeled off occurs from growth furnace inner surface Under carburizing situation (usual carburizing), [CO]/[CO₂]≤1, on the other hand, in the carburizing situation of the degree that carbon dirt can be triggered to peel off Under (excess carburizing state), [CO]/[CO₂] value increase to greater than 10 degree.To carbon monoxide and titanium dioxide in cleaning The concentration of carbon is monitored display：By to the cleaning time started and end time is adjusted so that [CO]/[CO₂]≤10, Can make in growth furnace excessive carburizing does not occur.

[embodiment]

Continuously carry out by using the CNT manufacture devices shown in Fig. 2 the CNT comprising formation process, growth operation Manufacturing process, has manufactured CNT orientation aggregations, has then carried out cleaning process.

In the manufacture of CNT orientation aggregations, continuously loaded on the guipure of CNT manufacture devices and formed as shown below The base material of catalyst, makes the transporting velocity of guipure constant, and CNT orientation aggregations have been manufactured on base material.

(base material)

As the flat-shaped substrate as base material, horizontal 500mm × vertical 500mm, Fe-Cr alloys of thickness 0.3mm is prepared The flat board of SUS430 (manufacture of JFE Steel Co., Ltd., the mass % of Cr 18).Using laser microscope to multiple portions of substrate The surface roughness of position is determined, as a result, 0.063 μm of arithmetic average roughness Ra ≈.

(catalyst is formed)

Catalyst is formd on aforesaid substrate as shown below.Three aluminium secondary butylate 1.9g are dissolved in 2- propyl alcohol 100mL (78g), and add the triisopropanolamine 0.9g as stabilizer and be allowed to dissolve, make the coating for forming pellumina Agent.By dip coating in 25 DEG C of room temperature, the environment of relative humidity 50%, it is coated with substrate above-mentioned for forming aluminum oxide The coating agent of film.As application conditions, employ substrate impregnated in for form pellumina coating agent in after, protect Hold 20 seconds, with the condition that the bailing speed of 10mm/sec pulls substrate out.Then, substrate has been carried out air-drying for 5 minutes.Connect , after substrate is heated 30 minutes in 300 DEG C of air ambient, be cooled to room temperature.Thus, thickness is formd on substrate The pellumina of 40nm.

Then, ferric acetate 174mg is dissolved in 2- propyl alcohol 100mL, and is added as the triisopropanolamine 190mg of stabilizer And be allowed to dissolve, make iron film coating agent.In 25 DEG C of room temperature, the environment of relative humidity 50%, formed by dip coating Have on the substrate of above-mentioned pellumina and be coated with iron film coating agent.As application conditions, employ and substrate be impregnated in into the painting of iron film After in application, kept for 20 seconds, with the condition that the bailing speed of 3mm/ seconds pulls substrate out.Then, 5 points have been carried out to substrate Clock is air-dried.Then, substrate is heated 30 minutes in 100 DEG C of air ambient.After heating, substrate is cooled to room temperature, obtained The base material of the iron film of thickness 3nm is formed with flat-shaped substrate.

(manufacturing condition)

The condition in each portion of CNT manufacture devices when CNT is manufactured is set as described in Table 7.Need explanation , in table 7, empty column part represents and is set.

[table 7]

The addition of activation of catalyst material is have adjusted in operation is grown.In operation is grown, the base in being manufactured to CNT Atmosphere near material is sampled, and adjusts the amount of moisture added as activation of catalyst material so that hydrogen, methane, second Each concentration of alkane reaches maximum.

As accumulation manufacturing time, with every growth furnace from the interval of about 5~6 hours or so to the state for not sending into base material It is interior to import the gas comprising water and carried out the eudiometry in growth furnace.Adjustment starts the opportunity of cleaning, causes in an oxidation Concentration rate [CO]/[CO of carbon and carbon dioxide₂] no more than 10 moment start cleaning.

(cleaning process)

It is essentially identical when being manufactured with CNT as the condition in each portion of CNT manufacture devices in cleaning process, only growing element 3 Condition changed as described in Table 8.

[table 8]

Gas concentration (hydrogen, carbon monoxide, carbon dioxide) in growth furnace in cleaning is monitored, according to its knot Really, the amount of moisture and the value of design temperature that are imported as clean gas are adjusted within the above range so that hydrogen concentration is most Possibly high and (2 [CO₂]+[CO])/[H₂] value be not less than 0.7.Further, in (2 [CO₂]+[CO])/[H₂] value be less than Terminated cleaning before 0.7.

Repeat manufacture and the cleaning process of CNT under these conditions.Hydrogen during the 4th cleaning process, carbon monoxide and The monitoring result of gas concentration lwevel is as shown in Figure 7.Each gas concentration shown in figure shown in Fig. 7 is (clear as described in Table 9 The clean time：Hour (H), gas concentration：Volume ppm).The amount of moisture in clean gas now is 1.5 volume %, growth furnace Design temperature is 867 DEG C.

[table 9]

Time	H₂	CO	CO₂	(2[CO₂]+[CO])/[H₂]	[CO]/[CO₂]
						0.1	439	25.8	192.9	0.94	0.13
1	435	15.2	213.8	1.02	0.07
						2	423	18.8	214.7	1.06	0.09
3	420	17.4	192.4	0.96	0.09
						4	418	18.6	191.2	0.96	0.10
5	373	21.7	166.1	0.95	0.13
						6	357	19.4	160.7	0.95	0.12
7	337	23.8	150.3	0.96	0.16
						8	333	21.4	139.3	0.90	0.15
9	298	23.1	129.2	0.95	0.18
						10	299	28.4	121.7	0.91	0.23
11	255	38.1	101.5	0.95	0.38
						12	257	38.6	93.1	0.87	0.41
13	245	34.7	83	0.82	0.42
						14	226	40.3	77.5	0.86	0.52
15	213	52.9	58.8	0.80	0.90
						16	197	52.5	48.4	0.76	1.08

In the cleaning process of all times, carry out cleaning and cause (2 [CO₂]+[CO])/[H₂] value fall more than 0.7 and Less than 1.3 scope, in addition, carrying out cleaning causes [CO]/[CO₂] value fall below 10.

In order to confirm the effect of cleaning, the one of the unstrpped gas ejection section of growing element is determined before and after each cleaning process The partly carburizing amount (the increased weight because of carburizing) of (1, shower nozzle), and visual examination has been carried out by range estimation.Carburizing amount Change is as shown in Figure 8.Carburizing amount is increasing weight/surface product representation.The carburizing amount shown in coordinate diagram shown in Fig. 8 is for example following (carburizing amount shown in table 10：mg/cm², cumulative operational time：Hour (H)).

[table 10]

Cumulative operational time	Carburizing amount
		0	0.000
324	1.499
		345	0.750
471	1.331
		489	0.612
623	1.231
		643	0.551
722	1.147
		788	0.619
974	1.476
		995	0.673
1117	1.239
		1141	0.558
1255	1.086
		1278	0.528
1442	1.285
		1460	0.497

Fallen in about 0.4~1.6mg/cm by the carburizing amount of shower nozzle²In the range of and the increased straight slope of carburizing amount (ooze Carbon speed) also keep substantially constant to understand in each time, by carrying out cleaning process as described herein, it can be determined that raw Excess carburizing and oxidation in stove long do not occur substantially.In addition, by the visual examination of shower nozzle it has been confirmed that being used as accumulation behaviour After making time operation about 60 days or so, be also not accompanied by excess carburizing carbon dirt come off.

In addition, being orientated the characteristic of aggregation, yield as the CNT for manufacturing in this embodiment：1.8~2.2mg/cm²、 BET specific surface area：1000~1300m²/ g, density：0.025~0.06g/cm³, external diameter：2.8~3.0nm (half-peak breadths：2nm)、 Carbon purity：More than 99.9%, Herman orientation factor：0.7th, the G/D ratios based on Raman spectroscopy：4~6.

As (manufacturing time accounting)=(manufacturing time)/{ (manufacturing time)+(cleaning time) }, embodiment is calculated Manufacturing time accounting.Its result is as shown in Figure 9.The manufacturing time accounting of the embodiment shown in the coordinate diagram shown in Fig. 9 and tired Product operating time (manufacturing time accounting as shown in following tables 11：%, cumulative operational time：Hour (H)).

[table 11]

Manufacturing time accounting	Cumulative operational time
		94	345
87	489
		87	643
89	788
		90	994
84	1141
		83	1278
90	1460

It can be seen from Fig. 9 and table 11, manufacturing time accounting basic scope 80~90% in embodiment is constant.

Industrial applicibility

The CNT obtained using manufacture method of the invention is suitable for electronic device material, optical element material, electric conductivity The fields such as material.

Claims

1. a kind of manufacture method of CNT, it is CNT is had the side grown on the base material of catalyst in area load Method, wherein, the manufacture method includes：

Growth operation, the unstrpped gas of CNT is supplied to the catalyst of the base material being sent in growth furnace, and And at least one of the catalyst and the unstrpped gas are heated, CNT is grown on the substrate； With

Cleaning process, to clean gas of the supply comprising water in the growth furnace, to being cleaned in the growth furnace,

The concentration of the hydrogen in gas in by the growth furnace is set to [H₂], the concentration of carbon dioxide be set to [CO₂], an oxygen When the concentration for changing carbon is set to [CO], in the cleaning process, to being cleaned in the growth furnace, so that meeting following formula (1)：

0.7≤{(2[CO₂]+[CO])/[H₂]}≤1.3···(1)。

2. the manufacture method of CNT according to claim 1, in the cleaning process, to entering in the growth furnace Row cleans, causes to meet following formula (2)：

0 ＜ ([CO]/[CO₂])≤10···(2)。

3. the manufacture method of CNT according to claim 1, wherein, at least a portion of the growth furnace includes gold Category.

4. the manufacture method of the CNT according to any one of claims 1 to 3, wherein, the cleaning process is included To (2 [the CO in the growth furnace₂]+[CO])/[H₂] be monitored.

5. the manufacture method of CNT according to claim 2, wherein, the cleaning process is included to the growth furnace Interior [CO]/[CO₂] be monitored.

6. the manufacture method of CNT according to claim 1, wherein, in the growth operation, to the base material The catalyst also supply activation of catalyst material in addition to supplying the unstrpped gas.